JPS6394224A - Spacer particle for display device and its production - Google Patents

Abstract

PURPOSE:To prevent movement of spacer particles in a display device by coating the surface of insulating material particles with synthetic resin powder so that the particles are securely fixed by the synthetic resin to the electrode substrate, etc. of the display device. CONSTITUTION:The surface of the inorg. insulating material particles 2 is coated with the synthetic resin powder 3. The synthetic resin powder 3 may be in the state in which a spherical state is maintained and the adjacent powder particles join to each other or may be, in some cases, in the state in which part of the powder is melted to form a thin film. The diameter (d) of the synthetic resin powder to coat the surface of the insulating material particles 2 is specified to <=D/5 when the diameter of the insulating material particles is designated as D. The diameter D of the insulating material particles correspond to the diameter of the spacer particles and is preferably 0.1-10mum. The movement of the spacer particles in the display device such as liquid crystal layer is thereby obviated and the dealing with a slight change in the thickness of the display device is permitted.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to spacer particles for display devices and a method for producing the same. The present invention relates to a spacer particle for a display device and a method for producing the same.

Technical background of the invention and its problems Liquid crystal display devices are widely used as display devices for watches, calculators, wall-mounted televisions, and the like.

This liquid crystal display is a display device that uses liquid crystal that changes the orientation of molecules and the direction of polarization by applying a slight voltage, and usually has a structure in which a liquid crystal layer is sandwiched between two electrodes. are doing.

In such a liquid crystal display device, it is desirable that the thickness of the liquid crystal layer be as thin as possible, and it is also desired that there be no variation in the thickness of the liquid crystal layer. If there are variations in the thickness of the liquid crystal layer, the electric field strength applied to the liquid crystal layer will be locally uneven, and the contrast ratio of the image will vary from place to place, causing unevenness in the image. In addition, the response speed of the liquid crystal to input signals changes depending on the thickness of the liquid crystal layer and the electric field strength, but if the thickness of the liquid crystal layer is uneven, there will be a difference in the response speed and a clear image will not be obtained. You will no longer be able to obtain it.

For this reason, in liquid crystal display devices, a thin and uniform liquid crystal layer is formed between the two electrode substrates by interposing a spacer made of a thin insulator between the two electrodes and filling the space with liquid crystal.

Spacers used in the above-mentioned liquid crystal display devices include abrasive aluminum oxide classified into 2 to 10 μm, glass fiber with a diameter of 2 to 1 m, and 50
Those cut into lengths of ~100 μm, or synthetic resins such as benzoguanamine shaped into spheres of 2 to 10 μm have been used.

Liquid crystal display devices using such conventionally known spacers do not pose any major problems when the size is small, but when the size becomes large, the following problems occur. is.

(a) Small liquid crystal display devices are often used with the display surface horizontal, so this is not a particularly big problem, but large liquid crystal display devices such as wall-mounted TVs, for example, is used vertically or obliquely, the spacer particles placed between the two electrodes gradually move downward due to their weight, resulting in uneven thickness of the liquid crystal layer and, in some cases, A dropout phenomenon occurs in which most of the spacer particles move downward and the thickness of the liquid crystal layer becomes significantly non-uniform, making it impossible to obtain a clear image.

('b) It is necessary to slightly change the thickness of the liquid crystal layer depending on the type of liquid crystal used, but it is possible to control the shape of the spacer to accommodate this subtle change in the thickness of the liquid crystal layer. Can not.

(C) The particle size distribution of the spacer particles is large, making it impossible to provide a liquid crystal layer with a uniform thickness, which may result in uneven images or color tone abnormalities.

(d> When using ferroelectric liquid crystal, it is necessary to make the thickness of the liquid crystal layer about 1 to 2 μm, but it is necessary to provide a spacer that can adjust the thickness of the liquid crystal layer to such a thickness. Doesn't exist.

(e) The spacer particles in the liquid crystal layer aggregate and the spacer is visible in the displayed image, or the long axis is 10 to 50 μm.
With this spacer, the spacer itself may be visible in the displayed image.

(f) Since the spacer particles are not spherical, the spacer or the transparent electrode may be damaged, resulting in a defective display device.

(g) If the spacer is made of resin, it is easily deformed by heating or pressure, making it impossible to provide a uniform liquid crystal layer thickness, and if the cell substrate thermally expands, As a result, the thickness of the liquid crystal layer may change, and spacer particles that were once fixed may move freely within the liquid crystal layer.

In particular, in order to solve the problems mentioned in (a), attempts have been made to electrostatically fix the polyimide alignment film and the spacer particles by surface treating the spacer particles made of an inorganic insulator. However, the effects cannot necessarily be said to be sufficient.

The present inventors have conducted intensive studies to solve the problems associated with such conventionally known spacer particles for display devices, especially the problem mentioned in (a), and found that the surface of the insulating material particles The particles coated with synthetic resin are securely fixed to the electrode substrate of the display device and do not move in the liquid crystal layer, and the particle size distribution obtained by a specific method is sharp, and the surface is made of synthetic resin. The present invention was completed by discovering that resin-coated particles can be used as spacers for display devices.

Purpose of the Invention The present invention is intended to solve the problems associated with the prior art as described above. An object of the present invention is to provide spacer particles for a display device that can respond to subtle changes in thickness, have a uniform thickness, and prevent spacer particles from aggregating with each other, and a method for manufacturing the same. There is.

Summary of the Invention The spacer particles for display devices according to the present invention are characterized in that the surfaces of the insulating material particles are coated with synthetic resin powder.

The first method for producing spacer particles for a display device according to the present invention is to add a metal alkoxide to a water-alcohol dispersion in which a metal oxide or metal hydroxide is dispersed as a seed while keeping the dispersion alkaline. The method is characterized in that the particles are added and hydrolyzed, the metal alkoxide decomposition products are deposited on the seeds to cause particle growth, and then the surfaces of the particles separated from the dispersion are coated with a synthetic resin.

Further, in the second method for producing spacer particles for a display device according to the present invention, a metal alkoxide is added to a water-alcohol dispersion in which a metal oxide or a metal hydroxide is dispersed as a seed while keeping the dispersion alkaline. A black color obtained by adding and hydrolyzing a metal alkoxide decomposition product onto the seed to cause particle growth, and then heat-treating the particles separated from the dispersion at a temperature of 250°C or higher. It is characterized by coating the surface of the particles with a synthetic resin.

In the spacer particles for display devices according to the present invention, since the surface of the insulating material particles is coated with synthetic resin powder,
Since the spacer particles are firmly fixed to the electrode substrate or the like of the display device by the synthetic resin, the spacer particles do not move within the display device.

Further, the spacer particles for a display device manufactured by the first manufacturing method according to the present invention have a sharp particle size distribution,
Moreover, it is possible to control the particle diameter to any desired size, and since the particles rarely aggregate with each other, it can respond to subtle changes in thickness, has a uniform thickness, and has spacer particles. It has the excellent property that it cannot be visually observed from the outside.

Furthermore, the spacer particles for display devices manufactured by the second manufacturing method according to the present invention are black in color and have a sharp particle size distribution, and the particle size can be controlled to any desired size. Moreover, since the particles rarely aggregate with each other, it can respond to subtle changes in thickness.
Moreover, it has an excellent property that it has a uniform thickness, the spacer particles are not visible from the outside, and an image with excellent contrast can be obtained.

Further, since the spacer particles according to the present invention are spherical, they do not damage the transparent electrode and do not undergo deformation due to heat or pressure. Since a metal alkoxide is used as a raw material, it also has the effect of producing a highly pure spacer.

DETAILED DESCRIPTION OF THE INVENTION The spacer particles for display devices and the method for manufacturing the same according to the present invention will be specifically described below.

In the spacer particle 1 for a display device according to the present invention, the surface of an inorganic insulating material particle 2 is coated with a synthetic resin powder 3, as shown in a schematic diagram in FIG.

Although almost the entire surface of the insulating material particles 2 is covered with the synthetic resin powder 3, it is not necessarily necessary that the entire surface is covered with the synthetic resin powder 3.

The synthetic resin powder 3 covering the surface of the insulating material particles 2 may be in a state in which adjacent powders are bonded to each other while maintaining a spherical shape, as shown in a schematic diagram in FIG. In some cases, a portion may be melted to form a thin film.

The diameter d of the synthetic resin powder covering the surface of the insulating material particles 2
is preferably D15 or less, preferably D/7 or less, specifically 0.01 to 2.0 μm, preferably 0.01 to 1.0 μm, where D is the diameter of the insulating material particles.
It is desirable that it is m. The diameter d of this synthetic resin powder 3
If D exceeds D15, the synthetic resin powder 3 may fall off the surface of the insulating material particles 2 due to its weight, which is not preferable.

Note that the diameter of the insulating material particles corresponds to the diameter of the spacer particles, and is preferably 0.1 to 10 μm.

The synthetic resin powder 3 has a glass transition point of 200°C.
The following thermoplastic synthetic resins or thermosetting synthetic resins having a curing temperature of 200° C. or less are used. Glass transition point is 2
Thermoplastic synthetic resin with a temperature exceeding 00℃ or a curing temperature of 2
A thermosetting synthetic resin with a temperature exceeding 00° C. is not preferable because a high temperature is required to fix the spacer particles in the display device.

As described briefly, when the spacer particles for a display device according to the present invention are used in a liquid crystal display device, they are mixed into a thermosetting sealing resin and provided on the peripheral edge of a display device substrate, and It is provided in the liquid crystal layer portion where sealing resin is not provided. At this time, the two substrates are bonded under heat and pressure. During this heating, the synthetic resin powder 3 provided on the surface of the insulating material particles 2 is melted, resulting in a thin synthetic resin layer 4 as shown in FIG. A pair of display device substrates 5a, 5 via
It is fixed to b. At this time, since the insulating material particles 2 and the display device substrates 5a, 5b are bonded by heat and pressure, there is no excess synthetic resin between the insulating material 2 and the display device substrates 5a, 5b. , only a very thin synthetic resin layer 4 is formed. It is considered that the molten synthetic resin accumulates on the side portions 6 of the insulating material particles 2. therefore,
In the present invention, the size of the insulating material particles 2 approximately corresponds to the size of the spacer particles. 'Next, a method for manufacturing spacer particles for display devices according to the present invention will be explained.

First, a water-alcohol dispersion in which metal oxides or metal hydroxides are dispersed as seeds is prepared. The seeds dispersed in the water-alcohol dispersion are metal oxide particles or metal hydroxide particles, but other particles with uniform particle sizes may be used depending on the case. The particles used as seeds as described above have a size of 0.05 to 9 μm.
It is preferable that the particle size is as uniform as possible.

To obtain such a water-alcohol dispersion in which seeds are dispersed, the seeds may be added to a water-alcohol mixed solution, or the seeds may be generated in the water-alcohol dispersion. Among these, a water-alcohol dispersion in which seeds obtained by hydrolyzing a metal alkoxide in a water-alcohol dispersion are dispersed is preferably used. Seed production methods include, for example, powder and powder metallurgy 23° (
4), 19-24 (1976) or Journal
lcolloid &Interface Sci,
26.62-69 (1968).

In this way, a water-alcohol dispersion in which metal oxide particles or metal hydroxide particles are dispersed as seeds is obtained. is added to form a stabilized dispersion (hereinafter sometimes referred to as heel sol). If the dispersion is not stabilized by adding an alkali, the seed particles may aggregate and precipitate. When the seeds agglomerate, metal alkoxide decomposition products also adhere to the joints (necks) of the agglomerated particles, making it impossible to obtain particles with a uniform particle size.

The alkali added to stabilize the dispersion is as follows:
Ammonia gas, aqueous ammonia, alkali metal hydroxides such as sodium hydroxide, quaternary ammonium salts, amines, etc. may be used alone or in combination.

The alcohol S degree in the water-alcohol dispersion in which the seeds are dispersed is preferably 35 to 97% by weight.

The alcohols used here include methanol, ethanol, n-propanol, isopropanol, n-propanol,
Lower alcohols such as butyl alcohol and isobutyl alcohol are used. Moreover, a mixed solvent of these lower alcohols can also be used.

In addition to water and alcohol, other organic solvents can also be used as the water-alcohol dispersion. As such an organic solvent, one is used that has good compatibility with water and alcohol, and also has good compatibility with metal alkoxide.

The concentration of the seeds in the water-alcohol dispersion is preferably 0.05 to 20.0% by weight in terms of oxide concentration. If the oxide concentration of the seeds is less than 0.05% by weight, new seeds may be generated in the subsequent process of attaching metal alkoxide decomposition products to the seeds.
This is not preferable because the particle size distribution of the obtained particles becomes broad.

On the other hand, if the equivalent oxide concentration of the seed exceeds 20.0% by weight, it is not preferable because the particles will aggregate during the step of adhering the metal alkoxide decomposition product to the seed.

Next, while keeping the heel sol alkaline, a metal alkoxide is added to the heel sol, which is a water-alcohol dispersion in which the alkali-stabilized seeds obtained as described above are dispersed, for hydrolysis. Seed particles are grown by depositing metal alkoxide decomposition products on the seeds.

As the metal alkoxide, any metal alkoxide can be used as long as it can form an alkoxide. The number of carbon atoms in the ester group forming the alkoxide is preferably about 1 to 7, preferably about 1 to 4. Such metal alkoxides may be used after being diluted with alcohol or the like, or may be used as a undiluted solution.

When adding a metal alkoxide to the dispersion, it is preferable to add a water-alcohol mixed solution together with the metal alkoxide. These metal alkoxides and water-alcohol mixed solution are preferably added gradually to the heel sol.

When a metal alkoxide is added to Healsol, the metal alkoxide begins to hydrolyze, and at this time, the pH of the solution rapidly increases.
H changes. If the heel sol liquid is no longer alkaline as described above, seeds may aggregate or new seeds may be generated, which is not preferable because the particle size distribution of the final particles becomes broad. Therefore, when adding the metal alkoxide, the heel sol is kept alkaline. The pH of the heel sol is preferably 10 to 13. In order to keep the heel sol alkaline, it is sufficient to add an alkali to the heel sol. Specifically, the added alkali includes ammonia gas, aqueous ammonia, amines, alkali metal hydroxides, and quaternary ammonium salts. Used alone or in combination.

The temperature at which the metal alkoxide is hydrolyzed is not particularly limited, but when a temperature higher than the boiling point of water or alcohol is used, it is preferable to pressurize the solution so that it can maintain a liquid phase. However, carrying out the decomposition reaction of the metal alkoxide above the critical temperature of alcohol or the like present in the reaction system may change the composition ratio in the liquid phase, so it is preferable to carry out the decomposition reaction below the critical temperature.

Seed particles are grown by depositing the metal alkoxide decomposition product on the seeds as described above, but the concentration of the grown particles in the reaction system is 0.05 to 2 in terms of oxide concentration.
It is preferably 0.0% by weight, more preferably 0.05 to 15.0% by weight. Particle concentration is 0.05% by weight
If the concentration is less than 1% by weight, productivity will be poor and a large amount of alcohol will be required, resulting in poor economic efficiency.On the other hand, if the concentration of particles exceeds 20% by weight, aggregation will occur between particles during seed particle growth, resulting in poor productivity. This is not preferable because the particle size distribution becomes broad.

When depositing the metal alkoxide decomposition product on the seeds, the alcohol concentration in the reaction system is preferably 35 to 97% by weight.

If the alcohol concentration is less than 35% by weight, it will have poor compatibility with the metal alkoxide to be added and will form an emulsion.
This is not preferable because the seeds may aggregate or amorphous particles that are not spherical may be obtained.
If it exceeds % by weight, the rate of hydrolysis of the metal alkoxide becomes too slow, which is not preferable. The alcohol concentration in the reaction system can be adjusted by adding water and alcohol together with the metal alkoxide into the reaction system,
The ratio of alcohol to the alkoxide is 0.4 to 1.1 moles, and the ratio of water to the alkoxide is 2.0 to 24 moles.
．． It is preferable that it is added in a proportion of 0 mol.

The particles thus obtained and dispersed in the water-alcohol dispersion medium are spherical and have a particle size of 0.1 to 10 um.
It has a sharp particle size distribution (±σ≦0.5) and is dispersed in the dispersion medium. In addition, according to the method for producing particles as described above, the particle size of the obtained particles is 0.1 to
It can be easily controlled to any value within 10 μm.

Furthermore, the concentration of particles in the dispersion medium based on oxides is 0.05.
~20.0% by weight, which can be significantly higher than in conventional methods of producing particles using metal alkoxides. Therefore, it is possible to increase the production efficiency of the particles and also to reduce the production cost.

In order to further increase the stability of the particles dispersed in the dispersion obtained in this way, if a stabilizer such as an alkali is added to the dispersion obtained and aging is performed, the dispersion will remain stable for a long period of time. The particles inside do not aggregate.

Next, the dispersion obtained as described above is dried according to a conventional method to obtain spherical particles with good dispersibility. The particles obtained at this stage are still white in color.

If black particles are required, the particles are then further heat-treated at a temperature of 250°C or higher, preferably 250 to 1000''C, in an air atmosphere or an inert gas atmosphere to form white particles. The color changes to black, and black particles with good dispersibility are obtained.

It is thought that the reason why white particles change to black particles by heat treatment at a temperature of 250° C. or higher is as follows. In other words, organic substances such as unreacted metal alkoxides are present inside the particles before heat treatment, and when these unreacted organic substances such as metal alkoxides are heated to a temperature of 250°C or higher and decomposed or carbonized, , the particles probably turn black.

As mentioned above, the heat treatment temperature for the white particles is 250'C or higher, preferably 250 to 1000'C. However, if the heat treatment temperature is lower than 250°C, the white particles will be blackened; This is not preferable because it takes a long time for the heat treatment to occur. On the other hand, if the heat treatment temperature exceeds 1000'C, sintering between particles may occur, which is not preferable.

Generally, when the particle size of white particles is small, 2
Blackening occurs by heat treatment at a relatively low temperature in the temperature range of 50 to 1000°C, but as the particle size increases, heat treatment at a relatively high temperature is required.

Furthermore, in the present invention, when adding the metal alkoxide to the water-alcohol dispersion in which the seeds are dispersed, an organic substance that is dissolved or dispersed in the water-alcohol dispersion is added, and this organic substance is By depositing the metal alkoxide decomposition product on the seed and then heat-treating the resulting particles to a temperature of 250° C. or higher, the color tone of the resulting black particles can be further blackened. Alternatively, before heat-treating the white particles obtained by drying the dispersion, the white particles can be impregnated with a solution of an organic substance to attach the organic substance to the particles, and then heat-treated. The color tone of the black particles can be further blackened.

Next, the surfaces of the white or black insulating material particles obtained as described above are coated with synthetic resin powder. In order to coat the surface of insulating material particles with synthetic resin powder, it is necessary to ensure that the insulating material particles coated with synthetic resin powder do not aggregate with each other and that the surface of each individual particle is coated almost uniformly with synthetic resin powder. Any method can be adopted as long as it is a method.

Examples include the following methods. ``When insulating material particles are placed in a dry atmosphere, they become electrically charged. For example, if the metal alkoxide used during production is silicon, titanium, zirconium, or tin, it will be negatively charged, and if the metal is aluminum, magnesium, or zinc, it will be positively charged. Spherical synthetic resin powder having an opposite charge to the insulating material particles charged in this manner is adsorbed by electrostatic force.

Although the synthetic resin powder is adsorbed on almost the entire surface of the insulating material particles, the binding force is weak due to electrostatic force, and the synthetic resin powder easily falls off. When an impact force is applied to the insulating material particles to which the synthetic resin powder has been adsorbed, and the heat generated at that time melts a portion of the synthetic resin, the synthetic resin powders are joined together and the synthetic resin powder becomes the insulating material particles. Fixed. In order to apply an impact force to the insulating material particles to which the synthetic resin powder has been adsorbed, such particles may be placed in a pulverizer such as a ball mill or a grinder, and the pulverizer may be operated.

In order to assemble a display device such as a liquid crystal display device using the thus obtained spacer particles for a display device as a spacer, a conventionally known method can be applied as is.

In the present invention, a display device is provided using the particles produced as described above as a spacer, but the display device can be used in addition to a liquid crystal display device, an erectrochromic display (EDC), a plasma display (PD
P), used in liquid crystal printers, touch panels, light modulation elements, etc.

Effects of the Invention In the spacer particles for display devices according to the present invention, the surface of the insulating material particles is coated with synthetic resin powder, so that the spacer particles are firmly fixed to the electrode substrate of the display device, etc. by the synthetic resin. Therefore, the spacer particles do not move within the display device.

Further, the spacer particles for a display device manufactured by the first manufacturing method according to the present invention have a sharp particle size distribution,
Moreover, it is possible to control the particle size to any desired size, and since the particles rarely aggregate with each other, it can respond to subtle changes in thickness, has a uniform thickness, and has spacer particles. It has the excellent property that it cannot be visually observed from the outside.

In addition, the spacer particles for display devices manufactured by the second manufacturing method according to the present invention are black in color and have a sharp particle size distribution, and the particle size can be controlled to any size. Moreover, since the particles rarely aggregate with each other, it can respond to subtle changes in thickness.
Moreover, it has an excellent property that it has a uniform thickness, the spacer particles are not visible from the outside, and an image with excellent contrast can be obtained.

Furthermore, since the spacer particles according to the present invention are spherical, they do not damage the transparent electrode and do not undergo deformation due to heat or pressure. Furthermore, since metal alkoxide is used as a raw material, a highly pure spacer can be obtained.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Ethyl alcohol 487! A mixed solution of J and 389 g of water was kept at 35° C. while stirring, and 71.7 g of ammonia gas was dissolved in this mixed solution. 17.4 g of 28% ethyl silicate was added to this, and stirring was continued for 2 hours.
A white cloudy liquid in which seed particles equivalent to 0.5% by weight as O2 were dispersed was obtained. 1. Immediately add NaOH,
Add 3.3 g of an aqueous solution in which 0.03 g of A
> obtained. 979 of this heel sol (A) was stirred and kept at 35°C, and while controlling the pH to 11.5 with ammonia gas, 455 g of ethyl alcohol and 88 g of water were mixed.
86g and 28% ethyl silicate 570
g was simultaneously added gradually over 19 hours. After adding Kanayama, add 103 g of an aqueous solution in which 1 g of NaOH was dissolved in the solution,
This was heated to 70°C and held for 2 hours to obtain a dispersion liquid (■).

While stirring the resulting dispersion (I) 111 at 35°C, adding ethyl alcohol 639 and water 519 and controlling the pH to 11.5 with ammonia gas, a mixture of ethyl alcohol 6389 and water 8149 and 28 % ethyl silicate was simultaneously added slowly over 19 hours.

Aqueous solution 6 in which NaOH0,79 is dissolved in the total addition condensate
5 g was added, and the mixture was heated to 70° C. and maintained for 2 hours to obtain a dispersion. While stirring, 94.6 g of this dispersion was kept at 65°C, 116 g of ethyl alcohol and 95 g of water were added, and while controlling the pH to 11.5 with ammonia gas, a mixture of 30'l of ethyl alcohol and 4389 of water and 28 g of water were added.
% ethylsilicate were simultaneously added gradually over a period of 19 hours. 65 g of an aqueous solution in which NaOH0.79 was dissolved was added to the total addition condensate, and this was heated to 70°C and held for 2 hours to obtain a dispersion (n). The resulting dispersion (I
I>1126g was kept at 35℃ with stirring, 155g of ethyl alcohol and 127g of water were added, and the pH was adjusted to 1 with ammonia gas.
Ethyl alcohol 16 while controlling to 1.5
A mixture of 49 and 275 g of water and 156 g of 28% ethyl silicate were simultaneously added gradually over 19 hours. Aqueous solution 6 in which 7 g of NaOHo was dissolved in the total addition condensate
5 g was added, and the mixture was heated to 70° C. and held for 2 hours to obtain a dispersion.

This dispersion liquid 13429 was kept at 65°C while stirring, and ethyl alcohol 1859 and water 151g were added to it, followed by purge with ammonia gas.
While controlling H to 11.5, add 93g of ethyl alcohol and 150g of water! ? The mixture and 82 g of 28% ethyl silicate were simultaneously added slowly over 19 hours. 58 g of an aqueous solution in which 6 g of Na0f-10.6 was dissolved was added to the total addition condensate, and this was heated to 70° C. and held for 2 hours to obtain a dispersion (III).

This dispersion (III) was dried at 110°C to form powder particles (
1) was separated. 95 g of the obtained powder particles and methyl methacrylate resin powder (manufactured by Souken Kagaku, trade name MP-100)
0.0 particle size: 0.4μ) and 5g' to adsorb the resin. Furthermore, the particles were placed in a ball mill and stirred to coat them with resin (powder particles (2)).

Next, sealing resin (manufactured by Mitsui Toatsu, epoxy resin>1
00g, powder particles (1) 1 obtained as above
An ink composition was prepared by dispersing g. The obtained ink composition was printed with a screen printer on the periphery of the alignment film of a laminate in which a transparent electrode and an alignment film were formed on a 2 cm x 2 cm polished glass substrate for a liquid crystal display device to form a large liquid crystal display. A display device substrate was obtained.

Next, ethyl alcohol (EtOH) lj km.

Powder particles (2) obtained as above 0.019
Disperse and use this dispersion at room temperature 60°C and humidity 3%.
It was sprayed onto the parts of a large liquid crystal display substrate placed in a spraying chamber maintained at a constant temperature, where the sealing resin was not provided. After pre-drying this at 90°C for 30 minutes, this was bonded to another large liquid crystal display substrate comprising a glass substrate with transparent electrodes and an alignment film.
The resin was cured by heating at 180"C for 11 hours under a pressure of /cra to prepare 100 cells for a large liquid crystal display device.

A liquid crystal as described later was injected into the portion of the cell for a large-sized liquid crystal display device obtained in this way, where the sealing resin was not applied, to obtain a large-sized liquid crystal display device.

Example 2 The powder particles 1) obtained in Example 1 were heat treated at 750'C in a nitrogen atmosphere for 3 hours to obtain black powder particles (
A cell for a large-sized liquid crystal display device was obtained in the same manner as Example 1 except that 3) was manufactured and the particles were used.

The shapes and population standard deviations of the spacer particles of Examples were measured.

Furthermore, the LCD cell obtained above was evaluated by the following method.

■The center, cloth, and left portions of the cell were cut using a diamond cutter, and the cell gap was measured using an electron microscope.

■The presence or absence of spacer coarse particles (agglomerated particles) in the image area was visually observed, and if even one coarse particle was visually observed, it was judged as a defective product.

(2) The operating status of an LCD obtained by injecting TN liquid crystal (manufactured by Merck & Co., Ltd.) and combining it with a polarizing film so that transmitted light can be obtained when an electric field is applied was confirmed.

Furthermore, the LCD cell was heated at 800 G in a centrifuge for 1 hour to make it easier for the spanner particles to move in the liquid crystal layer, and then the operating status was confirmed.

(2) A heat cycle test was conducted in which heating and cooling were repeated four times between -20°C and 80°C to confirm the operating status of the large liquid crystal display device.

The results are shown in Table 1.

[Brief explanation of the drawing]

FIG. 1 is a schematic explanatory diagram of spacer particles for a display device according to the present invention, and FIG. 2 is an explanatory diagram showing the state of adhesion between a substrate and the particles when these spacer particles are used. 1... Spacer particles for display device 2... Insulating material particles 3... Synthetic resin powder 5...
・Substrate agent Patent attorney Shunichi Meiki Figure 1 Drawing 1i (no changes to 3) Figure 2 February 7, 1988

Claims (1)

[Scope of Claims] 1) A spacer particle for a display device, characterized in that the surface of the insulating material particle is coated with synthetic resin powder. 2) A metal alkoxide is added to a water-alcohol dispersion in which a metal oxide or metal hydroxide is dispersed as a seed, while keeping the dispersion alkaline, and hydrolyzed to produce metal alkoxide decomposition on the seed. 1. A method for producing spacer particles for a display device, which comprises attaching a substance to the particles to cause particle growth, and then coating the surfaces of the particles separated from a dispersion with a synthetic resin. 3) A metal alkoxide is added to a water-alcohol dispersion in which a metal oxide or metal hydroxide is dispersed as a seed while keeping the dispersion alkaline and hydrolyzed, and metal alkoxide is decomposed and generated on the seed. It is characterized by coating the surface of the blackish particles obtained by attaching a substance to cause particle growth and then heat-treating the particles separated from the dispersion at a temperature of 250°C or higher with a synthetic resin, A method for producing spacer particles for display devices.